A Reactivity Study of Well-Defined Alkenylalanes Toward Anions, Lewis-Bases and Benzophenone

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Abstract
The reactivity of well-defined silyl-substituted alkenylalanes has been studied in the presence of anions, Lewis bases and benzophenone. In the presence of methyllithium or fluoride anions, the corresponding methyl- or fluoro-aluminates bearing alkenyl substituents of Z configuration have been fully characterized including by X-ray diffraction analysis. The configurational stability of these ate complexes toward Z-to-E isomerization revealed substituent-dependent and was examined on the basis of experiments and DFT calculations. In a second step, the fate of benzonitrile and ketone adducts of the alkenylalanes was investigated. Whereas the benzonitrile adducts revealed thermally stable, the corresponding Ph2C═O → Al(alkenyl)3 adducts evolved to the alkoxyaluminums due to the transfer of a α-hydride from an alkenyl substituent to the activated carbonyl function. The mechanism of this uncommon reduction could be unveiled and compared to more classical alkyl- and alkenyl-groups migration processes.
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  • CNRS Chimie

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